Supported catalyst containing tethered cation forming activator

ABSTRACT

A support for use in preparing supported catalysts for addition polymerizations comprising the reaction product of: (A) an inorganic oxide material comprising reactive surface hydroxyl groups, at least some of said hydroxyl groups optionally having been functionalized an converted to a reactive silano moiety corresponding to the formula: --OSiR 2  H, wherein R, independently each occurrence, is hydrogen C 1-20  hydrocarbyl, or C 1-20  hydrocarbyloxy, said inorganic oxide or functionalized derivative thereof comprising less than 1.0 mmol of reactive surface hydroxyl functionality per gram, and (B) an activator compound comprising: b 1 ) a cation which is capable of reacting with a transition metal compound to form a catalytically active transition metal complex, and b 2 ) a compatible anion containing at least one substituent able to react with the inorgnaic oxide, with residual hydroxyl functionality of the inorganic oxide, or with the reactive silane moiety, hereby covalently bonding the compatible anion to the support, catalysts formed therefrom, process of manufacture and the method to use.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims benefit of priority from provisional application60/007,609, filed Nov. 27, 1995, now abandonded.

This invention relates to supports and supported catalysts formedtherefrom that are useful for polymerization of olefins. Moreparticularly, the invention relates to such supports comprising anactivator compound that is chemically bound or tethered to the support.The invention also relates to the preparation of such support materialsand supported catalysts and to their use in an olefin polymerizationprocess.

Several supported cation forming catalysts for use in olefinpolymerization processes have been previously disclosed in the art.WO-91/09882 described a supported catalyst prepared by combining i) abis(cyclopentadienyl) metal compound containing at least one ligandcapable of reacting with a proton, ii) an activator component comprisinga cation capable of donating a proton and a bulky, labile anion capableof stabilizing the metal cation formed as a result of reaction betweenthe metal compound and the activator component, and iii) a catalystsupport material. The support material could be subjected to a thermalor chemical dehydration treatment. In some of the examplestriethylaluminum was added for this purpose. The maximum bulk density ofpolymers formed by use of the foregoing supported catalyst reported inWO91/09882 was 0.17 g/cm³. Catalyst efficiencies that were reported wereless than satisfactory for commercial application.

WO-94/03506 described a supported ionic catalyst prepared by combiningi) a monocyclopentadienyl metal compound, ii) an activator componentcomprising a cation which will irreversibly react with at least oneligand contained in said metal compound and an anion, said anion being achemically stable, non-nucleophilic, anionic complex, and iii) acatalyst support material. Optionally, the supported ionic catalystcould be prepolymerized with an olefinic monomer. The support materialcould also be treated with a hydrolyzable organoadditive, preferably aGroup 13 alkyl compound such as triethylaluminum. The reference alsotaught the use of such supported ionic catalysts in a gas phasepolymerization process. Disadvantageously, the catalyst efficienciesobtained in WO-94/03506, were likewise insufficient for commercial use.

In U.S. Pat. No. 5,399,636, supported metallocene catalysts wherein themetallocene was chemically attached to support materials, includingsilica, alumina, clay, phosphated alumina, and mixtures thereof, weredisclosed. In U.S. Pat. No. 5,427,991, certain catalyst supportscomprising polyanionic moieties constituted of noncoordinating anionicgroups chemically bonded to crosslinked polymeric core components weredisclosed. At column 19, lines 4-12 the reference taught thedesirability of masking or protecting hydroxyl groups on the substrateby using standard chemical treatments. However, masking or protectingthe hydroxyl groups prior to the reaction with the noncoordinatinganionic reactant renders them inert to further reaction, therebydefeating the purpose of the invention. Performing the masking orprotecting after reaction of the noncoordinating anionic reactantdetrimentally interferes with the desired chemically bonded anionicmoieties. In FIG. 8, an alternative scheme comprising functionalizingsurface hydroxyl groups by reaction with p-bromophenyl(trimethoxy)silanewas postulated. No teaching of the desirability of limiting the quantityof surface hydroxyl functionality of the silica to amounts less than 1.0mmol/g was provided. In addition no disclosure of forming reactivesilane functionality instead of p-bromophenylsiloxane functionality isprovided by the reference. For the foregoing reasons, the disclosure ofthis publication with respect to silica or alumina based startingmaterials is believed to be inoperable or deficient.

Cationic homogeneous catalysts prepared by the use of cation formingactivator compounds are disclosed in numerous prior art references. InEP-A-277,004 and U.S. Pat. No. 5,064,802 the use of Bronsted acid saltsable to form cations via hydrogen transfer is disclosed. InEP-A-277,003, a similar process using bulky anions containing multipleboron atoms is disclosed. In WO93/23412 carbonium salt cation formingactivators are disclosed. U.S. Pat. No. 5,321,106 taught the use ofoxidizing salt cationic activators and U.S. Ser. No. 304,314, filed Sep.12, 1994 taught the use of silylium salt cationic activators.Disadvantageously, such homogeneous catalysts when supported by normaltechniques of physical absorption on the surface of a support material,may be removed again by diluents found in common solution or slurrypolymerizations, and by diluents potentially found in gas phasepolymerization process, such as those employing condensation and recycleof either diluents or monomers. Such loss of the catalytic material fromthe support may detrimentally affect the bulk density of the resultingpolymeric product.

It would be desirable to provide a supported catalyst and apolymerization process using the same that is capable of producingolefin polymers at good catalyst efficiencies. It would further bedesirable to provide such a supported catalyst that is adapted for usein a slurry or gas phase polymerization process and is relativelyunaffected by the presence of condensed monomer or diluents.

In one aspect of the present invention there is provided a support foruse in preparing supported catalysts for addition polymerizationscomprising the reaction product of:

(A) an inorganic oxide material comprising a solid matrix, and reactivehydroxyl groups or reactive silane functionalized derivatives ofhydroxyl groups on the surface thereof, said reactive silanecorresponding to the formula: --OSiR₂ H, wherein R, independently eachoccurrence, is hydrogen, C₁₋₂₀ hydrocarbyl, or C₁₋₂₀ hydrocarbyloxy,said inorganic oxide material comprising less than 1.0 mmol of reactivesurface hydroxyl functionality per gram, and

(B) an activator compound comprising:

b₁) a cation which is capable of reacting with a transition metalcompound to form a catalytically active transition metal complex, and

b₂) a compatible anion containing at least one substituent able to reactwith the inorganic oxide matrix, with residual hydroxyl functionality ofthe inorganic oxide, or with the reactive silane moiety, therebycovalently bonding the compatible anion to the support.

In addition there is provided a supported catalyst system useful in theaddition polymerization of addition polymerizable monomers comprisingthe above identified support; and

(C) a transition metal compound containing at least one π-bonded anionicligand group, said transition metal compound being capable of reactingwith the aforementioned support by means of the cation b₁) to therebychemically bind the catalytically active transition metal complex andsupport.

In a further aspect, the invention provides a process for preparing asupport comprising combining an inorganic oxide material comprising asolid matrix, and reactive hydroxyl groups or reactive silanefunctionalized derivatives of hydroxyl groups on the surface thereof,said reactive silane corresponding to the formula: --OSiR₂ H, wherein R,independently each occurrence, is hydrogen, C₁₋₂₀ hydrocarbyl, or C₁₋₂₀hydrocarbyloxy, said inorganic oxide material comprising less than 1.0mmol of reactive surface hydroxyl functionality per gram, with anactivator compound (B) to form a support for an olefin polymerizationcatalyst.

In yet another aspect the invention provides an addition polymerizationprocess wherein one or more addition polymerizable monomers arecontacted with a supported catalyst system according to the presentinvention under addition polymerization conditions.

The supports and supported catalysts of the invention are readilyprepared in high yields and efficiencies. Importantly, catalyst systemsprepared from the foregoing catalyst components demonstrate improvedperformance as measured by catalyst activity and/or product bulkdensity, compared to previously known supported catalyst systems. Thisis believed to be a result of controlling the quantity of availablesurface hydroxyl groups of the inorganic oxide to less than 1.0 mmol pergram prior to reaction with the activator compound B, and/or the use ofthe specific reactive silane functional groups as further disclosedherein.

All references herein to elements or metals belonging to a certain Grouprefer to the Periodic Table of the Elements published and copyrighted byCRC Press, Inc., 1989. Also any reference to the Group or Groups shallbe to the Group or Groups as reflected in this Periodic Table of theElements using the IUPAC system for numbering groups.

Surprisingly, it has been found that using the unique combination ofactivator compounds and supports as specified herein, the activatorcompound can be attached to the support yet remain capable of activatingtransition metal catalysts typically employed in addition polymerizationprocesses. The present supported catalysts can be employed to produceolefin polymers at extremely high catalyst efficiencies. Preferably thecatalysts attain efficiencies of at least 1×10⁵ g polymer/g transitionmetal, more preferably at least 1×10⁶ g polymer/g transition metal.Moreover, these supported catalysts are highly immune to catalystsleaching under typical process conditions employed in gas phase orslurry polymerizations.

Additional benefits in the use of the present supported catalysts inpolymerization processes include the fact that the formation of polymerdeposits at reactor walls and other moving parts in the reactor isavoided and that polymers having improved bulk density are obtained inparticle forming polymerization processes. According to the presentinvention, improved bulk densities for ethylene containing homopolymersand interpolymers are bulk densities of at least 0.20 g/cm³, andpreferably of at least 0.25 g/cm³.

Suitable inorganic oxide supports for use in the present inventioninclude highly porous silicas, aluminas, aluminosilicates,aluminophosphates, clays, titanias, and mixtures thereof. Preferredinorganic oxides are alumina and silica. The most preferred supportmaterial is silica. The support material may be in granular,agglomerated, pelletized, or any other physical form.

Supports suitable for the present invention preferably have a surfacearea as determined by nitrogen porosimetry using the B.E.T. method from10 to 1000 m² /g, and preferably from 100 to 600 m² /g. The pore volumeof the support, as determined by nitrogen adsorption, advantageously isbetween 0.1 and 3 cm³ /g, preferably from 0.2 to 2 cm³ /g. The averageparticle size is not critical but typically is from 0.5 to 500 μm,preferably from 1 to 150 μm.

Inorganic oxides, especially silica, alumina and aluminosilicates areknown to inherently possess small quantities of hydroxyl functionalityattached to the atomic matrix. When used to prepare component Atherefrom, these materials are preferably first subjected to a heattreatment and/or chemical treatment to reduce the hydroxyl content to0.001-10 mmol/g, more preferably 0.01-1.0 mmol/g, most preferably0.1-0.8 mmol/g. Typical heat treatments (calcining) are carried out at atemperature from 150 to 900° C., preferably 300 to 850° C. for aduration of 10 minutes to 50 hours. Typical chemical treatments includecontacting with Lewis acid alkylating agents such as trihydrocarbylaluminum compounds, trihydrocarbylchlorosilane compounds,trihydrocarbylalkoxysilane compounds or similar agents. Residualhydroxyl functionality can be detected by the technique of FourierTransform Infrared Spectroscopy (DRIFTS IR) as disclosed in FourierTransform Infrared Spectroscopy, P. Griffiths & J. de Haseth, 83Chemical Analysis, Wiley Interscience (1986), p. 544.

The inorganic oxide may be unfunctionalized excepting for surfacehydroxyl groups as previously disclosed. In this embodiment of theinvention the low hydroxyl content of the support leads to superiorproperties of the resulting supported catalyst, most likely due to lackof interference with the transition metal complex by the residualhydroxyl groups. Preferred hydroxyl contents of such support are lessthan 0.8 mmol/g, preferably less than 0.5 mmol/g.

The inorganic oxide may also be functionalized by treating with asilane, hydrocarbyloxysilane, or chlorosilane functionalizing agent toattach thereto pendant reactive silane functionality, as previouslydisclosed. Suitable functionalizing agents are compounds that react withthe surface hydroxyl groups of the inorganic oxide or react with themetal or metalloid atoms of the inorganic oxide matrix. Examples ofsuitable functionalizing agents include phenylsilane, diphenylsilane,methylphenylsilane, dimethylsilane, diethylsilane, diethoxysilane, andchlorodimethylsilane. Techniques for forming such functionalizedinorganic oxide compounds were previously disclosed in U.S. Pat. Nos.3,687,920 and 3,879,368.

In a preferred embodiment the silane and the inorganic oxide arecontacted, optionally in the presence of a hydrocarbon diluent, in thepresence of a base assist, preferably a C₁₋₄ trialkylamine. The reactionis conducted at a temperature from 0 to 110° C., preferably from 20 to50° C. Generally an excess of functionalizing agent is employed.Preferred ratios of functionalizing agent based on inorganic oxide arefrom 1 to 2500 mmol/g. As a result of the foregoing functionalizingreaction, residual hydroxyl functionality of the inorganic oxide isfurther reduced to the previously mentioned low level of less than 1.0mmol/g. Preferably, the residual hydroxyl content of functionalizedsupports is less than 0.8 mmol/g, and most preferably less than 0.5mmol/g. Highly preferably in preparing component A, a calcined silica isemployed having initial (i. e. prefunctionalized) residual hydroxylcontent less than 1.0 mmol/g, and from 1 to 20 mmol of functionalizingagent/g silica is employed. The molar ratio of base assist employed tofunctionalizing agent is generally from 0.7:1 to 2.0:1. Unreactedfunctionalizing agent is preferably removed from the surface of theinorganic oxide, for example, by washing with a liquid hydrocarbon, andthe support is thoroughly dried prior to use in preparing supportedcatalyst systems.

The inorganic oxide, the resulting support, or the supported catalystsystem may also be treated with an aluminum component selected from analumoxane or an aluminum compound of the formula AlR₃, wherein R is aspreviously defined. Examples of suitable R groups include methyl,methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers),butyl (all isomers), butoxy (all isomers), phenyl, and benzyl.Preferably, the aluminum component is selected from the group consistingof aluminoxanes and tri(C₁₋₄ hydrocarbyl)aluminum compounds. Mostpreferred aluminum components are aluminoxanes, trimethyl aluminum,triethyl aluminum, triisobutyl aluminum, and mixtures thereof.

Alumoxanes (also referred to as aluminoxanes) are oligomeric orpolymeric aluminum oxy compounds containing chains of alternatingaluminum and oxygen atoms, whereby the aluminum carries a substituent,preferably an alkyl group. The structure of alumoxane is believed to berepresented by the following general formulae (--Al(R)--O)_(m), for acyclic alumoxane, and R₂ Al--O(--Al(R)--O)_(m) --AlR₂, for a linearcompound, wherein R is as previously defined, and m is an integerranging from 1 to 50, preferably at least 4. Alumoxanes are typicallythe reaction products of water and an aluminum alkyl, which in additionto an alkyl group may contain halide or alkoxide groups. Reactingseveral different aluminum alkyl compounds, such as for exampletrimethyl aluminum and tri-isobutyl aluminum, with water yieldsso-called modified or mixed alumoxanes. Preferred alumoxanes aremethylalumoxane and methylalumoxane modified with minor amounts of C₂₋₄alkyl groups, especially isobutyl. Alumoxanes generally contain minor tosubstantial amounts of starting aluminum alkyl compound.

Particular techniques for the preparation of alumoxane type compounds bycontacting an aluminum alkyl compound with an inorganic salt containingwater of crystallization are disclosed in U.S. Pat. No. 4,542,119. In aparticular preferred embodiment an aluminum alkyl compound is contactedwith a regeneratable water-containing substance such as hydratedalumina, silica or other substance. This is disclosed in EP-A-338,044.Thus the alumoxane may be incorporated into the support by reaction of ahydrated alumina or silica material, which has optionally beenfunctionalized with silane, siloxane, hydrocarbyloxysilane, orchlorosilane groups, with a tri(C₁₋₁₀ alkyl) aluminum compound accordingto known techniques.

A treatment of the inorganic oxide material in order to also includeoptional alumoxane or trialkylaluminum loadings in addition to activatorcompound involves contacting the same before, after or simultaneouslywith addition of the activator compound hereunder with an alumoxane ortrialkylaluminum compound, especially triethylaluminum ortriisobutylaluminum. Optionally the mixture can also be heated under aninert atmosphere for a period and at a temperature sufficient to fixalumoxane or trialkylaluminum to the support, or the support componentcontaining alumoxane or the trialkylaluminum compound may be subjectedto one or more wash steps to remove alumoxane or trialkylaluminum notfixed to the support.

Besides contacting the support with alumoxane the alumoxane may begenerated in situ by contacting an unhydrolyzed inorganic oxide or amoistened inorganic oxide with a trialkyl aluminum compound optionallyin the presence of an inert diluent. Such a process is well known in theart, having been disclosed in EP-A-250,600, U.S. Pat. Nos. 4,912,075,and 5,008,228. Suitable aliphatic hydrocarbon diluents include pentane,isopentane, hexane, heptane, octane, isooctane, nonane, isononane,decane, cyclohexane, methylcyclohexane and combinations of two or moreof such diluents. Suitable aromatic hydrocarbon diluents are benzene,toluene, xylene, and other alkyl or halogen substituted aromaticcompounds. Most preferably, the diluent is an aromatic hydrocarbon,especially toluene. After preparation in the foregoing manner theresidual hydroxyl content thereof is reduced to the desired low levelless than 1.0 mmol of OH per gram of support, by any of the previouslydisclosed techniques.

The anionic component of the activator compound B used according to thepresent invention corresponds to the formula:

    [DM'Q.sub.3 ].sup.-

wherein:

D is a linking group comprising functionality capable of reaction withthe inorganic oxide matrix, with residual hydroxyl functionalitythereof, or with reactive silane functional groups of the optionallyfunctionalized inorganic oxide,

M' is boron or aluminum in an oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms.

Most preferably, Q is each occurrence a fluorinated aryl group,especially, a pentafluorophenyl group.

Preferred activator compounds are salts of the formula

    G.sup.+e [DM'Q.sub.3 ].sup.-.sub.e,

wherein G^(+e) is the cationic remnant of a Bronsted acid salt, anoxidizing cation, a carbonium ion or a silylium ion; and e is an integerfrom 1 to 3, most preferably 1.

Suitable linking substituents, D, on compatible anions used withunmodified inorganic oxides or with inorganic oxide containing onlyresidual hydroxyl functionality, include moieties bearing silane,siloxane, hydrocarbyloxysilane, halosilane, amino, carboxylic acid,carboxylic acid ester, aldehyde, ketone or epoxide functionality,containing from 1 to 1×10⁶ nonhydrogen atoms, more preferably from 2 to1000 nonhydrogen atoms, and most preferably 4 to 20 nonhydrogen atoms.In practice, use of silane containing compatible anions may require useof a base catalyst, such as a tri(C₁₋₄ alkyl)amine, to effect thereaction with a substrate containing only residual hydroxylfunctionality. Preferably D for use with such unmodified inorganic oxidecompounds is a silane or chlorosilane substituted hydrocarbyl radical.Preferred linking substituents, D, include silyl-substituted aryl,silyl-substituted aralkyl, silyl-substituted alkaryl, silyl-substitutedalkyl, silyl-substituted haloaryl, or silyl-substituted haloalkylgroups, including polymeric linking groups, most preferablyp-silylphenyl (--C₆ H₄ SiH₃), p-silyltetrafluorophenyl (--C₆ F₄ SiH₃),silylnaphthyl (--C₁₀ H₈ SiH₃), silylperfluoronaphthyl (--C₁₀ F₈ SiH₃),and 2-silyl-1-ethyl(--C₂ H₄ SiH₃), groups.

Suitable linking substituents, D, on compatible anions used withinorganic oxides that have been modified with reactive silanefunctionality include moieties bearing silane, siloxane,hydrocarbyloxysilane, halosilane, hydroxyl, thiol, amino, carboxylicacid, carboxylic acid ester, aldehyde, ketone or epoxide functionalitycontaining from 1 to 1×10⁶ nonhydrogen atoms, more preferably from 2 to1000 nonhydrogen atoms, and most preferably 4 to 20 nonhydrogen atoms.Preferably D, in such circumstances is a hydroxyl substitutedhydrocarbyl radical, more preferably a hydroxy-substituted aryl,hydroxy-substituted aralkyl, hydroxy-substituted alkaryl,hydroxy-substituted alkyl, hydroxy-substituted haloaryl, orhydroxy-substituted haloalkyl group including polymeric linking groups,most preferably hydroxyphenyl, hydroxytolyl, hydroxybenzyl,hydroxynaphthyl, hydroxybisphenyl, hydroxycyclohexyl, C₁₋₄ hydroxyalkyl,and hydroxy-polystyryl groups, or fluorinated derivatives thereof. Amost preferred linking substituent, D, is a p-hydroxyphenyl,4-hydroxybenzyl, 6-hydroxy-2-naphthyl group, 4-(4'-hydroxyphenyl)phenyl,4-((4'-hydroxyphenyl)dimethylmethylene)phenyl, or fluorinatedderivatives thereof. A base catalyst, such as a tri(C₁₋₄ alkyl)amine,may also be used to assist in the reaction with the substrate.

Most highly preferably, D is one of the foregoing hydroxy substitutedsubstituents used in combination with a reactive silane functionalizedsilica.

Illustrative, but not limiting, examples of anionic components, [DM'Q₃]⁻, of activator compounds to be used in the present invention includetris(pentafluorophenyl)(4-hydroxyphenyl)borate,tris(pentafluorophenyl)(4-hydroxytetrafluorophenyl)borate,tris-(2,4-difluorophenyl)(4-hydroxyphenyl)borate,tris-(3,5-difluorophenyl)(4-hydroxyphenyl)borate,tris-(3,5-di-trifluoromethylphenyl)(4-hydroxyphenyl)borate,tris(pentafluorophenyl)(2-hydroxyethyl)borate,tris(pentafluorophenyl)(4-hydroxybutyl)borate,tris(pentafluoro-phenyl)(4-hydroxycyclohexyl)borate,tris(pentafluorophenyl)(3,5-dimethyl-4-hydroxyphenyl)borate,tris(pentafluorophenyl)4-(4'-hydroxyphenyl)phenylborate, andtris(pentafluorophenyl)hydroxynaphthylborate (all isomers, especiallytris(pentafluorophenyl) (6-hydroxy-2-naphthyl)borate.

The cationic portion of the activator compound can be any cation whichis capable of reacting with the transition metal compound to form acatalytically active transition metal complex. Preferably the cation isselected from the group consisting of Bronsted acid cations, carboniumcations, silylium cations, and cationic oxidizing agents.

Bronsted acidic cations may be represented by the following generalformula:

    (L*--H).sup.+

wherein:

L* is a neutral Lewis base, preferably a nitrogen, phosphorus, oxygen,or sulfur containing Lewis base; and (L*--H)⁺ is a Bronsted acid.

Illustrative, but not limiting, examples of Bronsted acidic cations ofactivator compounds to be used in the present invention aretrialkyl-substituted ammonium cations such as triethylammonium,tripropylammonium, tri(n-butyl)ammonium, trimethylammonium,tributylammonium. Also suitable are N,N-dialkyl anilinium cations suchas N,N-dimethylanilinium, N,N-diethylanilinium,N,N-2,4,6-pentamethylanilinium and the like; dialkyl ammonium cationssuch as di-(i-propyl)ammonium, dicyclohexylammonium and the like; andtriaryl phosphonium cations such as triphenylphosphonium,tri(methylphenyl)phosphonium, tri(dimethylphenyl)phosphonium,diethyloxonium, dimethylsulphonium, diethylsulphonium, anddiphenylsulphonium.

A second type of suitable cation (depicted as ©⁺) is a stable carboniumor silylium ion containing up to 30 nonhydrogen atoms, the cation beingcapable of reacting with a substituent of the transition metal compoundand converting it into a catalytically active transition metal complex.Suitable examples of carbonium cations include tropyllium,triphenylmethylium, and benzene(diazonium) cations. Silylium salts havebeen previously generically disclosed in J. Chem Soc. Chem. Comm., 1993,383-384, as well as Lambert, J. B., et al., Organometallics, 1994, 13,2430-2443. Preferred silylium cations are trimethylsilylium,triethylsilylium and ether substituted adducts thereof.

Another suitable type of cation (depicted as Ox^(e+)) is a cationicoxidizing agent having a charge of e+, and e is an integer from 1 to 3.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, and Pb²⁺.

The activator compounds to be used in the present invention are readilyprepared by combining a Group 1, Group 2 or Grignard metal derivative ofthe functionalizing substituent, D, or a masked derivative thereof witha neutral precursor to the anion and thereafter contacting this reactionproduct with the chloride salt of the cation to be utilized. Examples ofsuitable metal derivatives include lithium or Grignard salts. The term"masked derivative" refers to the well known practice of utilizing aninert functionality during the preparation and converting the same tothe desired, reactive functionality in a subsequent step by methodswhich are well known by those skilled in the art. For example, atrimethylsiloxy group may be present during the synthesis andsubsequently converted to the desired hydroxyl group by hydrolysis.

The support of the present invention generally comprises from 0.001 to10 mmol of activator compound per gram of inorganic oxide, preferablyfrom 0.01 to 1 mmol/g. At too high amounts of activator compound, thesupport becomes expensive. At too low amounts the catalyst efficiency ofthe resulting supported catalyst becomes unacceptable. Residual hydroxylcontent after reaction with the activator compound is desirably lessthan 50 mole percent based on desired transition metal complex loading,more preferably less than 10 mole percent based on desired transitionmetal complex loading, most preferably less than 1 mole percent based ondesired transition metal complex loading.

The support of the present invention can be stored or shipped underinert conditions as such or slurried in an inert diluent, such as alkaneor aromatic hydrocarbons. It may be used to generate the supportedcatalyst of the present invention by contacting with a suitabletransition metal compound optionally in the presence of a liquiddiluent.

Suitable transition metal compounds (C) for use in the supportedcatalyst of the present invention may be derivatives of any transitionmetal including Lanthanides, but preferably of Group 3, 4, or Lanthanidemetals which are in the +2, +3, or +4 formal oxidation state meeting thepreviously mentioned requirements. Preferred compounds include metalcomplexes containing from 1 to 3π-bonded anionic ligand groups, whichmay be cyclic or noncyclic delocalized π-bonded anionic ligand groups.Exemplary of such π-bonded anionic ligand groups are conjugated ornonconjugated, cyclic or non-cyclic dienyl groups, allyl groups, andarene groups. By the term "π-bonded" is meant that the ligand group isbonded to the transition metal by means of a π bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhalogen, hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substitutedmetalloid radicals wherein the metalloid is selected from Group 14 ofthe Periodic Table of the Elements. Included within the term"hydrocarbyl" are C₁₋₂₀ straight, branched and cyclic alkyl radicals,C₆₋₂₀ aromatic radicals, C₇₋₂₀ alkyl-substituted aromatic radicals, andC₇₋₂₀ aryl-substituted alkyl radicals. In addition two or more suchradicals may together form a fused ring system or a hydrogenated fusedring system. Suitable hydrocarbyl-substituted organometalloid radicalsinclude mono-, di- and trisubstituted organometalloid radicals of Group14 elements wherein each of the hydrocarbyl groups contains from 1 to 20carbon atoms. Examples of suitable hydrocarbyl-substitutedorganometalloid radicals include trimethylsilyl, triethylsilyl,ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, andtrimethylgermyl groups.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, and decahydroanthracenylgroups, as well as C₁₋₁₀ hydrocarbyl-substituted derivatives thereof.Preferred anionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl,2,3-dimethylindenyl, fluorenyl, 2-methylindenyl and2-methyl-4-phenylindenyl.

Suitable transition metal compounds C) may be any derivative of anytransition metal including Lanthanides, but preferably of the Group 3,4, or Lanthanide transition metals. More preferred are metal complexescorresponding to the formula:

    L.sub.l MX.sub.m X'.sub.n X".sub.p, or a dimer thereof

wherein:

L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 nonhydrogen atoms, optionally two L groups may bejoined together through one or more substituents thereby forming abridged structure, and further optionally one L may be bound to Xthrough one or more substituents of L;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is an optional, divalent substituent of up to 50 non-hydrogen atomsthat together with L forms a metallocycle with M;

X' is an optional neutral Lewis base having up to 20 non-hydrogen atoms;

X" each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally, two X" groups may be covalently boundtogether forming a divalent dianionic moiety having both valences boundto M, or form a neutral, conjugated or nonconjugated diene that isπ-bonded to M (whereupon M is in the +2 oxidation state), or furtheroptionally one or more X" and one or more X' groups may be bondedtogether thereby forming a moiety that is both covalently bound to M andcoordinated thereto by means of Lewis base functionality;

l is 1 or 2;

m is 0 or 1;

n is a number from 0 to 3;

p is an integer from 0 to 3; and

the sum, l+m+p, is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two L groups.The latter complexes include those containing a bridging group linkingthe two L groups. Preferred bridging groups are those corresponding tothe formula (ER*₂)_(x) wherein E is silicon or carbon, R* independentlyeach occurrence is hydrogen or a group selected from silyl, hydrocarbyl,hydrocarbyloxy and combinations thereof, said R* having up to 30 carbonor silicon atoms, and x is 1 to 8. Preferably, R* independently eachoccurrence is methyl, benzyl, tert-butyl or phenyl.

Examples of the foregoing bis(L) containing complexes are compoundscorresponding to the formula: ##STR1## wherein: M is titanium, zirconiumor hafnium, preferably zirconium or hafnium, in the +2 or +4 formaloxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X" independently each occurrence is an anionic ligand group of up to 40nonhydrogen atoms, or two X" groups together form a divalent anionicligand group of up to 40 nonhydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms forming a π-complex with M,whereupon M is in the +2 formal oxidation state, and

R*, E and x are as previously defined.

The foregoing metal complexes are especially suited for the preparationof polymers having stereoregular molecular structure. In such capacityit is preferred that the complex possess Cs symmetry or possess achiral, stereorigid structure. Examples of the first type are compoundspossessing different delocalized π-bonded systems, such as onecyclopentadienyl group and one fluorenyl group. Similar systems based onTi(IV) or Zr(IV) were disclosed for preparation of syndiotactic olefinpolymers in Ewen, et al., J. Am. Chem. Soc. 110, 6255-6256 (1980).Examples of chiral structures include bis-indenyl complexes. Similarsystems based on Ti(IV) or Zr(IV) were disclosed for preparation ofisotactic olefin polymers in Wild et al., J. Organomet. Chem, 232,233-47, (1982).

Exemplary bridged ligands containing two π-bonded groups are:(dimethylsilyl-bis-cyclopentadienyl),(dimethylsilyl-bis-methylcyclopentadienyl),(dimethylsilyl-bis-ethylcyclopentadienyl,(dimethylsilyl-bis-t-butylcyclopentadienyl),(dimethylsilyl-bis-tetramethylcyclopentadienyl),(dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl),(dimethylsilyl-bis-fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl),(dimethylsilyl-bis-2-methyl-4-phenylindenyl),(dimethylsilyl-bis-2-methylindenyl),(dimethylsilyl-cyclopentadienyl-fluorenyl),(1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl),(1,2-bis(cyclopentadienyl)ethane, and(isopropylidene-cyclopentadienyl-fluorenyl).

Preferred X" groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X" groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X" groups are C₁₋₂₀hydrocarbyl groups.

A further class of metal complexes utilized in the present inventioncorrespond to the formula:

    L.sub.l MX.sub.m X'.sub.n X".sub.p, or a dimer thereof

wherein:

L is an anionic, delocalized, π-bonded group that is bound to M,containing up to 50 nonhydrogen atoms;

M is a metal of Group 4 of the Periodic Table of the Elements in the +2,+3 or +4 formal oxidation state;

X is a divalent substituent of up to 50 non-hydrogen atoms that togetherwith L forms a metallocycle with M;

X' is an optional neutral Lewis base ligand having up to 20 non-hydrogenatoms;

X" each occurrence is a monovalent, anionic moiety having up to 20non-hydrogen atoms, optionally two X" groups together may form adivalent anionic moiety having both valences bound to M or a neutralC₅₋₃₀ conjugated diene, and further optionally X' and X" may be bondedtogether thereby forming a moiety that is both covalently bound to M andcoordinated thereto by means of Lewis base functionality;

l is 1 or 2;

m is 1;

n is a number from 0 to 3;

p is an integer from 1 to 2; and

the sum, l+m+p, is equal to the formal oxidation state of M.

Preferred divalent X substituents preferably include groups containingup to 30 nonhydrogen atoms comprising at least one atom that is oxygen,sulfur, boron or a member of Group 14 of the Periodic Table of theElements directly attached to the delocalized π-bonded group, and adifferent atom, selected from the group consisting of nitrogen,phosphorus, oxygen or sulfur that is covalently bonded to M.

A preferred class of such Group 4 metal coordination complexes usedaccording to the present invention correspond to the formula: ##STR2##wherein: M is titanium or zirconium in the +2 or +4 formal oxidationstate;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X" is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, saidgroup having up to 20 nonhydrogen atoms, or two X" groups together forma C₅₋₃₀ conjugated diene;

Y is --O--, --S--, --NR*--, --PR*--; and

Z is SiR*₂, CR*₂, SiR*₂ SiR*₂, CR*₂ CR*₂, CR*═CR*, CR*₂ SiR*₂, or GeR*₂,wherein: R* is as previously defined.

Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention include:

cyclopentadienyltitaniumtrimethyl,

cyclopentadienyltitaniumtriethyl, cyclopentadienyltitaniumtriisopropyl,

cyclopentadienyltitaniumtriphenyl,

cyclopentadienyltitaniumtribenzyl,

cyclopentadienyltitanium-2,4-pentadienyl,cyclopentadienyltitaniumdimethylmethoxide,

cyclopentadienyltitaniumdimethylchloride,pentamethylcyclopentadienyltitaniumtrimethyl,

indenyltitaniumtrimethyl,

indenyltitaniumtriethyl,

indenyltitaniumtripropyl,

indenyltitaniumtriphenyl,

tetrahydroindenyltitaniumtribenzyl,

pentamethylcyclopentadienyltitaniumtriisopropyl,pentamethylcyclopentadienyltitaniumtribenzyl,

pentamethylcyclopentadienyltitaniumdimethylmethoxide,

pentamethylcyclopentadienyltitaniumdimethylchloride,

(η⁵ -2,4-dimethyl-1,3-pentadienyl)titaniumtrimethyl,

octahydrofluorenyltitaniumtrimethyl,

tetrahydroindenyltitaniumtrimethyl,

tetrahydrofluorenyltitaniumtrimethyl,

(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl,

(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)titaniumtrimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium dichloride,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium dimethyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl,

(tert-butylamido)(tetramethyl-η⁵ -indenyl)dimethylsilanetitaniumdimethyl,

(tert-butylamido)(tetramethyl-η⁵ -cyclopentadienyl)dimethylsilanetitanium (III) 2-(dimethylamino)benzyl;

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III) allyl,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)1,3-butadiene,

(tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)1,3-pentadiene,

(tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV) dimethyl,

(tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)1,4-diphenyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (IV) 1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)1,4-dibenzyl-1,3-butadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II) 2,4-hexadiene,

(tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II) 3-methyl-1,3-pentadiene,

(tert-butylamido)(2,4-dimethyl-1,3-pentadien-2-yl)dimethyl-silanetitaniumdimethyl,

(tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,and

(tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl.

Bis(L) containing complexes including bridged complexes suitable for usein the present invention include:

biscyclopentadienylzirconiumdimethyl,

biscyclopentadienyltitaniumdiethyl,

biscyclopentadienyltitaniumdiisopropyl,

biscyclopentadienyltitaniumdiphenyl,

biscyclopentadienylzirconium dibenzyl,

biscyclopentadienyltitanium-2,4-pentadienyl,biscyclopentadienyltitaniummethylmethoxide,

biscyclopentadienyltitaniummethylchloride,bispentamethylcyclopentadienyltitaniumdimethyl,

bisindenyltitaniumdimethyl,

indenylfluorenyltitaniumdiethyl,

bisindenyltitaniummethyl(2-(dimethylamino)benzyl),

bisindenyltitanium methyltrimethylsilyl,

bistetrahydroindenyltitanium methyltrimethylsilyl,

bispentamethylcyclopentadienyltitaniumdiisopropyl,

bispentamethylcyclopentadienyltitaniumdibenzyl,

bispentamethylcyclopentadienyltitaniummethylmethoxide,

bispentamethylcyclopentadienyltitaniummethylchloride,

(dimethylsilyl-bis-cyclopentadienyl)zirconiumdimethyl,

(dimethylsilyl-bis-pentamethylcyclopentadienyl)titanium-2,4-pentadienyl,

(dimethylsilyl-bis-t-butylcyclopentadienyl)zirconiumdichloride,

(methylene-bis-pentamethylcyclopentadienyl)titanium(III)2-(dimethylamino)benzyl,

(dimethylsilyl-bis-indenyl)zirconiumdichloride,

(dimethylsilyl-bis-2-methylindenyl)zirconiumdimethyl,

(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconiumdimethyl,

(dimethylsilyl-bis-2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,

(dimethylsilyl-bis-2-methyl-4-phenylindenyl)zirconium (II)1,4-diphenyl-1,3-butadiene,

(dimethylsilyl-bis-tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene,

(dimethylsilyl-bis-fluorenyl)zirconiumdichloride,

(dimethylsilyl-bis-tetrahydrofluorenyl)zirconiumdi(trimethylsilyl),

(isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and

(dimethylsilylpentamethylcyclopentadienylfluorenyl)zirconiumdimethyl.

Other compounds which are useful in the preparation of catalystcompositions according to this invention, especially compoundscontaining other Group 4 metals, will, of course, be apparent to thoseskilled in the art.

Generally, the ratio of moles of activator compound (B) to moles oftransition metal compound (C) in the supported catalyst is from 0.5:1 to2:1, preferably from 0.5:1 to 1.5:1 and most preferably from 0.75:1 to1.25:1. At too low ratios the supported catalyst will not be veryactive, whereas at too high ratios the catalyst cost becomes excessivedue to the relatively large quantities of activator compound utilized.The quantity of transition metal complex chemically bound to theinorganic oxide matrix in the resulting supported catalyst is preferablyfrom 0.0005 to 20 mmol/g, more preferably from 0.001 to 10 mmol/g.

The supported catalyst of the present invention can be prepared bycombining the support material, the activator compound and the metalcomplex in any order. Preferably, the inorganic oxide material is firsttreated with the activator compound by combining the two components in asuitable liquid diluent, such as an aliphatic or aromatic hydrocarbon toform a slurry. The temperature, pressure, and contact time for thistreatment are not critical, but generally vary from -20° C. to 150° C.,from 1 Pa to 10,000 MPa, more preferably at atmospheric pressure (100kPa), for 5 minutes to 48 hours. Usually the slurry is agitated. Afterthis treatment the solids are typically separated from the diluent.

Before using the support of the invention, the diluent or solvent ispreferably removed to obtain a free flowing powder. This is preferablydone by applying a technique which only removes the liquid and leavesthe resulting solid, such as by applying heat, reduced pressure,evaporation, or a combination thereof. Alternatively, the support may befurther contacted with the transition metal compound (C) prior toremoving the liquid diluent. If so contacted the transition metalcompound is preferably used dissolved in a suitable solvent, such as aliquid hydrocarbon solvent, advantageously a C₅₋₁₀ aliphatic orcycloaliphatic hydrocarbon or a C₆₋₁₀ aromatic hydrocarbon.Alternatively, a suspension or dispersion of the transition metalcompound in a nonsolvent may also be used. The contact temperature isnot critical provided it is below the decomposition temperature of thetransition metal and of the activator. Good results are obtained in atemperature range of 0 to 100° C. The contact may be total immersion inthe liquid medium or contact with an atomized spray of the solution,dispersion or suspension. All steps in the present process should beconducted in the absence of oxygen and moisture. The resulting supportedcatalyst may be stored or shipped in free flowing form under inertconditions after removal of the solvent.

The supported catalysts of the present invention may be used in additionpolymerization processes wherein one or more addition polymerizablemonomers are contacted with the supported catalyst of the inventionunder addition polymerization conditions.

Suitable addition polymerizable monomers include ethylenicallyunsaturated monomers, acetylenic compounds, conjugated or non-conjugateddienes, and polyenes. Preferred monomers include olefins, for examplesalpha-olefins having from 2 to 20,000, preferably from 2 to 20, morepreferably from 2 to 8 carbon atoms and combinations of two or more ofsuch alpha-olefins. Particularly suitable alpha-olefins include, forexample, ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene,1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, or combinationsthereof, as well as long chain vinyl terminated oligomeric or polymericreaction products formed during the polymerization, and C₁₀₋₃₀ α-olefinsspecifically added to the reaction mixture in order to producerelatively long chain branches in the resulting polymers. Preferably,the alpha-olefins are ethylene, propene, 1-butene, 4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethylene and/or propene with oneor more of such other alpha-olefins. Other preferred monomers includestyrene, halo- or alkyl substituted styrenes, tetrafluoroethylene,vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene, ethylidenenorbornene, and 1,7-octadiene. Mixtures of the above-mentioned monomersmay also be employed.

The supported catalyst can be formed in situ in the polymerizationmixture by introducing into said mixture both a support of the presentinvention, or its components, as well as a suitable transition metalcompound (C). The supported catalyst can be advantageously employed in ahigh pressure, solution, slurry or gas phase polymerization process. Ahigh pressure process is usually carried out at temperatures from 100 to400° C. and at pressures above 500 bar. A slurry process typically usesan inert hydrocarbon diluent and temperatures of from 0° C. up to atemperature just below the temperature at which the resulting polymerbecomes substantially soluble in the inert polymerization medium.Preferred temperatures are from 40° C. to 115° C. The solution processis carried out at temperatures from the temperature at which theresulting polymer is soluble in an inert solvent up to 275° C.,preferably at temperatures of from 130° C. to 260° C., more preferablyfrom 150° C. to 240° C. Preferred inert solvents are C₁₋₂₀ hydrocarbonsand preferably C₅₋₁₀ aliphatic hydrocarbons, including mixtures thereof.The solution and slurry processes are usually carried out at pressuresbetween 100 kPa to 10 MPa. Typical operating conditions for gas phasepolymerizations are from 20 to 100° C., more preferably from 40 to 80°C. In gas phase processes the pressure is typically from 10 kPa to 10MPa. Condensed monomer or diluent may be injected into the reactor toassist in heat removal by means of latent heat of vaporization.

Preferably for use in gas phase polymerization processes, the supporthas a median particle diameter from 20 to 200 μm, more preferably from30 μm to 150 μm, and most preferably from 50 μm to 100 μm. Preferablyfor use in slurry polymerization processes, the support has a medianparticle diameter from 1 to 200 μm, more preferably from 5 μm to 100 μm,and most preferably from 20 μm to 80 μm. Preferably for use in solutionor high pressure polymerization processes, the support has a medianparticle diameter from 1 to 40 μm, more preferably from 1 μm to 30 μm,and most preferably from 1 μm to 20 μm.

In the polymerization process of the present invention, scavengers maybe used which serve to protect the supported catalyst from catalystpoisons such as water, oxygen, and polar compounds. These scavengers aregenerally used in varying amounts depending on the amounts ofimpurities. Preferred scavengers include the aforementionedorganoaluminum compounds of the formula AlR₃ or alumoxanes.

In the present polymerization process, molecular weight control agentscan also be used. Examples of such molecular weight control agentsinclude hydrogen, trialkyl aluminum compounds or other known chaintransfer agents. A particular benefit of the use of the presentsupported catalysts is the ability (depending on reaction conditions) toproduce narrow molecular weight distribution α-olefin homopolymers andcopolymers. Preferred polymers have Mw/Mn of less than 2.5, morepreferably less than 2.3. Such narrow molecular weight distributionpolymer products, especially those from a slurry process are highlydesirable due to improved tensile strength properties.

Having described the invention the following examples are provided asfurther illustration thereof and are not to be construed as limiting.Unless stated to the contrary all parts and percentages are expressed ona weight basis. The bulk density of the polymers produced was determinedaccording to ASTM 1895.

EXAMPLES Example 1 A1a. Synthesis of (4-bromophenoxy)trimethylsilaneBrC₆ H₄ -p-OSiMe₃

1,1,1,3,3,3-hexamethyldisilazane (100 ml; 98 percent purity; 0.464 mol)was added to BrC₆ H₄ -p-OH (40.3 g; 0.116 mol) and heated to reflux for2 hours. After cooling to 25° C., the excess1,1,1,3,3,3-hexamethyldisilazane was separated by distillation (120° C.)and the residue purified by flash chromatography using silica (Davison948, 800° C., pentane). The product was a colorless liquid. Yield: 50 g(88 percent)

A1b. Synthesis of MgBrC₆ H₄ -p-OSiMe₃

Magnesium turnings (1.20 g; 49.4 mmol) were mixed with THF (4 ml)followed by 1,2-dibromoethane (0.25 ml; 2.87 mmol) in a 100 ml 3-neckedflask. The mixture began to reflux, and a solution of4-bromophenoxytrimethylsilane (7.5 ml; 38.8 mmol) in THF (32 ml) wasadded dropwise through a syringe over a period of 15 minutes. Theresulting reaction mixture was further refluxed for 1 hour and thencooled to 25° C. The dark gray solution was filtered and titrated with2-butanol in the presence of 5-methyl-1,10-phenanthroline. Yield: 81percent (0.87 M, 36 ml).

A1c. Synthesis of [MgBr.2THF][(C₆ F₅)₃ B(C₆ H₄ -p-OSiMe₃)]

A solution of B(C₆ F₅)₃ (15.85 g; 31 mmol) in 100 ml diethyl ether wastreated with freshly prepared MgBrC₆ H₄ -p-OSiMe₃ (35.5 ml; 0.87 M inTHF) at room temperature. The reaction mixture was stirred for 16 hours,100 ml pentane was added and the mixture further stirred for 30 minutesto form a two layer mixture. The upper pentane layer was decanted andthe lower layer was further washed with pentane (50 ml) two times. Theresulting syrup was evaporated under reduced pressure to obtain thewhite solid product. Yield: 22.1 g (77 percent) ¹ H NMR (d⁸ -THF) δ+0.18(s, 9H, --SiMe₃), 6.45 (d, 2H, C₆ H₄), 7.06 (d, 2H, C₆ H₄). ¹⁹ F (d⁸-THF) δ-131.1 (d), -167.2 (t), -169.9 (t). ¹⁹ C (d⁸ -THF) δ+0.46 (s,--SiMe₃), 117-153 (C_(aryl))

A1d. Synthesis of dimethylanilinium(4-hydroxyphenyl)tris(penta-fluorophenyl)borate [PhMe₂ NH][(C₆ F₅)₃ B(C₆H₄ -p-OH)]

[MgBr2THF][(C₆ F₅)₃ B(C₆ H₄ -p-OSiMe₃)] (22.1 g; 23.9 mmol) and aqueousNMe₂ PhHCl solution (100 ml; 0.312 M; 31.2 mmol) were stirred at roomtemperature for 16 hours. The resulting H₂ O solution was carefullydecanted and the viscous solid was washed with distilled H₂ O (6×150 ml)and rinsed with pentane (3×100 ml) and dried under reduced pressure.Yield: 13.2 g (76 percent). ¹ H NMR (d⁸ -THF) δ+3.22 (s, 6H, --NHMe₂Ph), 6.40 (d, 2H, C₆ H₄), 7.05 (d, 2H, C₆ H₄), 7.4-7.7 (m, 5H, NHMe₂Ph). ¹⁹ F (d⁸ -THF) δ-131.1 (d), -167.8(t), -169.9(t). ¹⁹ C (d⁸ -THF)δ+46.3 (NHMe₂ Ph), 112-158 (C_(aryl)).

A2a. Synthesis of 4-((4'-bromophenyl)phenoxy)trimethylsilane BrC₆ H₄--C₆ H₄ -p-OSiMe₃

1,1,1,3,3,3-Hexamethyldisilazane (75 ml; 98 percent purity; 0.348 mol)was added to BrC₆ H₄ --C₆ H₄ -p-OH (30 g; 0.117 mol) and heated toreflux for 4 hours. After cooling to 25° C., the solid product wasfiltered and rinsed with cold pentane (50 ml; 0° C.). The crude productwas then dissolved in diethylether and purified by flash chromatographyof silica (Davison 948, 800° C., pentane). The product was a whitecrystalline solid. Yield: 33.6 g (89 percent)

A2b. Synthesis of MgBrC₆ H₄ --C₆ H₄ -p-OSiMe₃

Magnesium powder (50 mesh; 0.47 g; 19.3 mmol) was mixed with THF (5 ml)in a 3-necked flask. 1,2-dibromoethane (0.25 ml; 2.87 mmol) was thensyringed into the flask and heated to reflux vigorously. A THF solution(11 ml) of BrC₆ H₄ --C₆ H₄ -p-OSiMe₃ (3.0 g; 9.34 mmol) was addeddropwise through a syringe over a period of 20 minutes under refluxconditions. The resulting hot reaction mixture was cooled to 25° C. in1.5 hours. The dark gray solution was filtered and titrated with2-butanol in the presence of 5-methyl-1,10-phenanthroline. Yield: 87percent (0.76 M, 10.9 ml).

A2c. Synthesis of [MgBr.2THF][(C₆ F₅)₃ B(C₆ H₄ --C₆ H₄ -p-OSiMe₃)]

A solution of B(C₆ F₅)₃ (3.24 g; 6.33 mmol) in 50 ml diethyl ether wastreated with freshly prepared MgBrC₆ H₄ --C₆ H₄ -p-OSiMe₃ (10.4 ml; 0.76M; 8.13 mmol) at room temperature. The resulting mixture was stirred for3 hours, worked up, and recovered following the procedure of Example3A1c). Yield: 6.84 g (84 percent)

A2d. Synthesis of dimethylanilinium4-((4'-hydroxyphenyl)phenyl)-tris(pentafluorophenyl)borate[PhMe₂ NH]⁺[(C₆ F₅)₃ B(C₆ H₄ --C₆ H₄ -p-OH)]⁻

The procedure of 1A1d) is substantially repeated. Yield: 84 percent

A3a. Preparation of 2-bromo-6-trimethylsiloxynaphthalene

A slurry of 10.0 g 2-bromo-6-naphthol in 30 mL Me₃ SiNHSiMe₃ was stirredunder argon for 2 hours. At this time, the excess silane reagent wasremoved under reduced pressure. The remaining solids were dissolved in20 mL pentane and eluted down a 2 inch (5 cm) pad of silica. The solventwas removed under reduced pressure yielding 11.5 g of2-bromo-6-trimethylsiloxynaphthalene as a white, crystalline solid. ¹ HNMR (CDCl₃): -0.40 (s, 9 H, SiMe₃), 6.4-7.3 (m, 6 H, aromatic H) ppm.

A3b. Preparation of6-(trimethylsiloxy-2-naphthyl)tris(pentafluoro-phenyl)borate MgBr₂.(Et₂O)_(x) (MgBr₂ (Et₂ O)_(x) [6-Me₃ SiOC₁₀ H₆ -2-B(C₆ F₅)₃ ])

A slurry of 0.7 g Mg powder in 10 mL THF was activated by addition of0.1 mL BrCH₂ CH₂ Br and heated to a gentle reflux. A solution of 5.0 g2-bromo-6-trimethylsiloxynaphthalene in 5 mL THF was added over a 30minute period. At this time a 0.5 mL aliquot of the cooled solution wastitrated with isopropyl alcohol. The remaining 13.9 mL of 0.758 MGrignard solution was added to a slurry of 5.39 g [B(C₆ F₅)₃ ] in 30 mLEt₂ O. The mixture was stirred for 20 hours, during which time a whiteprecipitate formed. The solids were collected by filtration, washed withEt₂ O and pentane, and dried under reduced pressure. Yield: 6.81 g MgBr₂(Et₂ O)x[6-Me₃ SiOC₁₀ H₆ -2-B(C₆ F₅)₃ ]. ¹ H NMR (THF-d₈): 0.28 (s, 9 H,SiMe3), 6.8-7.7 (m, 6 H, aromatic H) ppm. ¹⁹ F{¹ H} NMR (THF-d8): -123.0(d, J_(F-F) =19,5 Hz, ortho F), -159.4 (m, meta F), -161.9 (t, J_(F-F)=23 Hz, para F).

A3c. Preparation of dimethylanilinium(6-hydroxy-2-naphthyl)tris(penta-fluorophenyl)borate PhMe₂ NH⁺ [6-HOC₁₀H₆ -2-B(C₆ F₅)₃ ]⁻

The 6.81 g MgBr₂ (Et₂ O)x[6-Me₃ SiOC₁₀ H₆ -2-B(C₆ F₅)₃ ] prepared abovewere slurried in distilled water with an excess of PhMe₂ NHCl for 4hours. The water solution was decanted and the solids washed withseveral portions of distilled water. The resulting solids were dissolvedin 10 mL methanol. The methanol was subsequently removed under reducedpressure to yield PhMe₂ NH[6-HOC₁₀ H₆ -2-B(C₆ F₅)₃ ] as a white,crystalline solid. Yield: 4.34 g. ¹ H NMR (THF-d₈): 3.02 (6 H, NMe₂),6.6-7.5 (11 H, aromatic H) ppm. ¹⁹ F{1H} NMR (THF-d₈): -123.1 (d,J_(F-F) =20.6 Hz, ortho F), -159.4 (m, meta F), -161.8 (t, J_(F-F) =23Hz, para F).

B. Preparation of phenylsilane modified silica (PhH₂ Si--O-Silica)

A pentane (150 ml) slurry of 10 g of Davison™ 948 (800° C.) silica(available from Davison division of Grace Chemical Co.) was treated withphenylsilane (PhSiH₃) (2.70 g; 0.025 mol) and triethylamine (NEt₃) (2.53g; 0.025 mol) via a syringe under argon atmosphere at 23° C. Hydrogengas evolved from the solution vigorously. The resulting mixture wasagitated for 12 h. The phenylsilane-modified silica was collected on afrit under argon, washed with pentane (5×5 ml), and dried under reducedpressure. Yield was 10.43 g. DRIFTS IR: n (Si--H) 2178 cm⁻¹ (vs). ²⁹ SiCPMAS: δ-23 ppm. Hydroxyl content of the functionalized silica wasundetectable (<0.1 mmol./g)

C. Preparation of the supported anilinium borate ([NHMe₂ Ph]⁺ [(C₆ F₅)₃B (C₆ H₄ -p-O--SiHPh--O-Silica)]⁻

An ether (30 ml) slurry of phenylsilane-modified silica (3.00 g) wastreated with 100 ml of an ether solution of [NHMe₂ Ph]⁺ [(C₆ F₅)₃ B(C₆H₄ -p-OH)]⁻ (1.05 g; 1.44 mmol) at room temperature under an argonatmosphere. Hydrogen gas evolved from the solution for 10 min. Thesolution was stirred for 15 h and the resulting white solid wasfiltered, washed with ether (5×20 ml) and pentane (3×20 ml), and driedunder reduced pressure. Yield was 3.71 g. DRIFTS IR: n (Si--H) 2190 cm⁻¹(m); n (N--H) 3239 cm⁻¹ (s). ²⁹ Si CPMAS: --O--SiHPh-OSilica (s, -41ppm). ¹³ C CPMAS: NHMe₂ Ph (s, 48.5 ppm).

D. Slurry Batch Reactor Polymerization

A 2 liter autoclave reactor was evacuated at 80° C. overnight prior touse. A heptane (300 ml) slurry of phenylsilanefunctionalized-silica-supported anilinium(4-hydroxyphenyl)tris(pentafluorophenyl) borate, ([NHMe₂ Ph]⁺ [(C₆ F₅)₃B (C₆ H₄ -p-O--SiHPh-OSilica)]⁻) (200 mg), was treated with(t-butylamido)dimethyl (tetramethyl-η⁵ -cyclopentadienyl)-silanetitaniumdimethyl(10 mg; 31 mmol). The catalyst mixture was transferred viavacuum into the preheated reactor. Ethylene was quickly admitted to 200psig (1.4 Mpa) and the reactor temperature was maintained at 75° C. viaa recirculating water bath. Ethylene was fed on demand via a mass flowcontroller. Polyethylene yield after 10 minutes reaction was 7.14 g.Mw=745,600, Mw/Mn=2.465.

Example 2 A. The activator of example 1A1d was employed B. Preparationof diphenylsilane-modified silica (Ph₂ HSi--O-Silica)

A pentane (200 ml) slurry of Davison™ 948 (800° C.) silica (20.0 g) wastreated with Ph₂ SiH₂ (8.67 g; 0.047 mol) and NEt₃ (5.08 g; 0.050 mol)via a syringe under argon at room temperature. Hydrogen gas evolved fromthe solution vigorously. The resulting mixture was agitated for 12 h.The diphenylsilane-modified silica was collected on a frit under argon,washed with pentane (5×10 ml), and dried under reduced pressure. Yield:20.87 g. DRIFTS IR: n (Si--H) 2169 cm⁻¹ (m). Residual hydroxyl contentwas undetectable (<0.1 mmol/g silica).

C. Preparation of the diphenylsilane functionalized silica supportedanilinium (4-phenyl)tris(pentafluorophenyl)borate ([NHMe₂ Ph]⁺ [(C₆ F₅)₃B (C₆ H₄ -p-O--SiPh₂ --O-Silica)]⁻

A diethylether (30 ml) slurry of diphenylsilane-modified silica (3.00 g)was treated with a diethylether (100 ml) solution of [NHMe₂ Ph]⁺ [(C₆F₅)₃ B (C₆ H₄ -p-OH)]⁻ (1.00 g; 1.38 mmol) at room temperature under anargon atmosphere. The solution was stirred for 15 h and the resultingwhite solid was filtered, washed with ether (5×20 ml) and pentane (3×20mnl), and dried under reduced pressure. Yield was 3.11 g.

D1. Slurry Batch Reactor Polymerization

A 1 gallon Hoppes autoclave purchased from Autoclave Engineers Inc. wasinitially charged with 1850 grams of anhydrous hexane. The reactor vaporspace was then swept twice with a 5 mol percent hydrogen/ethylene gasmixture and vented between each sweep. The reactor was then brought upto 80° C. temperature and then vented to the solvent vapor pressure of13 psig (190 kPa). The hydrogen/ethylene mixture was then added toincrease the reactor pressure to 53 psig. (470 kPa). Ethylene wassupplied by a demand feed regulator with a set pressure of 180 psig.(1.3 MPa). The slurry catalyst was prepared by mixing 0.07 g of thediphenylsilane-modified silica supported anilinium borate, [NHMe₂ Ph]⁺[(C₆ F₅)₃ B (C₆ H₄ -p-O--SiPh₂ -OSilica)]⁻), 20 ml of mixed alkanessolvent (Isopar E™ available from Exxon Chemicals Inc., and 0.21 ml(0.0717M, 15 mmol) of a solution of(t-butyl)amidodimethyl(tetramethyl-η⁵ -cyclopentadienyl)silanetitaniumdimethyl and stirring for 15 minutes. The catalyst slurry was theninjected into the reactor via a stainless steel pressurized cylinder.After 60 minutes, the polymer sample was removed from the reactor,filtered, and the powder placed in a drying tray in a vacuum oven at 80°C. for approximately 30 minutes. 20.4 g of polyethylene was isolated(29,800 gPE/gTi).

D2. Solution Batch Reactor Polymerization

A stirred, one gallon autoclave reactor was charged with 1445 g ofIsopar E™ and 126 g of 1-octene and heated to 130° C. The reactor wasthen charged with 37 psig (360 kPa) of hydrogen followed by ethylenesufficient to bring the total pressure to 450 psig. (3.1 Mpa) Thecatalyst was prepared by stirring 0.15 g of the diphenylsilane-modifiedsilica supported anilinium borate, [NHMe₂ Ph]⁺ [(C₆ F₅)₃ B(C₆ H₄-p-O--SiPh₂ -OSilica)]⁻, 20 ml of Isopar E™, and 0.42 ml of a solutionof (t-butyl)amidodimethyl(tetramethyl-η⁵-cyclopentadienyl)-silanetitanium dimethyl (0.0717M, 30 mmol) for 15minutes. The catalyst slurry was injected into the reactor and thereactor temperature and pressure maintained by continually feedingethylene during the polymerization and cooling the reactor as required.After 10 minutes, the reactor contents were transferred into a nitrogenpurged resin kettle containing 0.2 g of antioxidant (Irganox 1010available from Ciba Geigy Co.). The sample was dried for 15 h in avacuum oven to yield 93.4 g of copolymer (65,000 gPE/gTi).

Example 3 B1. Preparation of phenylsilane-modified silica, PhH₂Si-OSilica

Silicas having residual hydroxyl content of 0.5 mmol/g were obtained bycalcining various silicas at 800° C. (Davison 948, Davison 952, andSylopol™-2212, available from GRACE Davison Corporation). 20.0 g of thecalcined silicas was slurried in pentane (150 ml) and treated withPhSiH₃ (6 ml; 0.048 mol) and triethylaluminum (6 ml; 0.043 mol) addedvia a syringe under argon atmosphere at room temperature. Hydrogen gasevolved from the solution vigorously. The resulting mixture was agitatedin a shaker for 12 hours. The phenylsilane-modified silicas werecollected on a frit under argon, washed with pentane (5×20 ml), anddried under reduced pressure. Yields were approximately 21.0 g. DRIFTSIR: v (Si--H) 2178 cm-1 (vs). ²⁹ Si CPMAS: δ-23 ppm. Residual hydroxylcontents were undetected (<0.1 mmol/g silica).

B2. Preparation of dimethylsilane-modified silica, Me₂ HSi-OSilica

A pentane (200 ml) slurry of GRACE Davison 948 (800 C; 0.5 mmol --OH/g)silica (30.0 g) was treated with (Me₂ HSi)₂ NH (3.0 g; 22.5 mmol). Theresulting mixture was agitated in a shaker for 12 hours. Thedimethylsilane-modified silica was collected on a frit under argon,washed with pentane (5×20 ml), and dried under reduced pressure. Yield:30.95 g. DRIFTS IR: v (SiH) 2158 cm-1 (s). ²⁹ Si CPMAS: δ-1.3 ppm.

B3. Preparation of diethylsilane-modified silica, Et₂ HSi-OSilica

A toluene (50 ml) slurry of GRACE Davison 948 (800 C; 0.5 mmol --OH/g)silica (2.5 g) was treated with Et₂ H₂ Si (0.90 g; 97 percent; 10.2mmol) and NEt₃ (1.05 ml; 7.5 mmol). The resulting mixture was refluxedfor 12 hours. The resulting solution was cooled to 25 C. and thediethylsilane-modified silica product was collected on a frit underargon, washed with pentane (5×20 ml), and dried under reduced pressure.Yield: 2.7 g. DRIFTS IR: v (Si--H) 2141 cm⁻¹ (s). ²⁹ Si CPMAS: δ+5 ppm.

B4. Preparation of phenylmethylsilane-modifled silica, PhMeHSi-OSilica

A heptane (350 ml) slurry of GRACE Davison 948 (800° C.; 0.5 mmol--OH/g) silica (30.0 g) was treated with PhMeH₂ Si (9.15 g; 97 percent;72.8 mmol) and NEt₃ (10.5 ml; 75 mmol). The resulting mixture wasrefluxed for 12 hours in an overhead stirrer under argon atmosphere. Theresulting solution was cooled to 25 C. and thephenylmethylsilane-modified silica product was collected on a frit underargon, washed with pentane (5×30 ml), and dried under reduced pressure.Yield: 31.73 g. DRIFTS IR: v (Si--H) 2160 cm⁻¹ (s). ²⁹ Si CPMAS: δ-6ppm.

B5. Preparation of diphenyisilane-modified silica, Ph₂ HSi-OSilica

A pentane (150 ml) slurry of GRACE Davison 948 (800° C.; 0.5 mmol--OH/g) silica (20.0 g) was treated with Ph₂ SiH₂ (9 ml; 98 percent;44.7 mmol) and NEt₃ (6.2 ml; 44.5 mmol) through syringe under argonatmosphere at room temperature. Hydrogen gas evolved from the solutionvigorously. The resulting mixture was agitated in a shaker for 12 hours.The diphenylsilane-modified silica product was collected on a frit underargon, washed with pentane (5×30 ml), and dried under reduced pressure.Yield: 21.6 g. DRIFTS IR: v (Si--H) 2169 cm⁻¹ (s).

C1. Preparation of the silica-supported anilinium borate, w/phenylsilanefunctionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄ -p-O--SiHPh-OSilica)]⁻

An ether (100 ml) slurry of phenylsilane-modified silica (preparedaccording to 3B1) (10.00 g) was treated with an ether (100 ml) solutionof dimethylanilinium (4-hydroxyphenyl)tris(penta-fluorophenyl)borate[PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ -p-OH)] (prepared according to 1A1(a-d))(2.94 g; 4.03 mmol) at room temperature under an argon atmosphere. Thesolution was agitated in dry box for 1.5 days and the resulting whitesolid was filtered off, washed with ether (5×20 ml) and pentane (3×20ml), and dried under reduced pressure. Yield: 11.99 g. DRIFTS IR: v(Si--H) 2190 cm⁻¹ (m); v (N--H) 3239 cm⁻¹ (w). ²⁹ Si CPMAS:--O--SiHPh-OSilica (s, -41 ppm). ¹³ C CPMAS: NHMe₂ Ph (s, 48.5 ppm). ICPboron content: 0.231 percent.

C2. Preparation of the silica-supported anilinium borate,w/di-methylsilane functionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄-p-O--SiMe₂ -Osilica))⁻

An ether (100 ml) slurry of dimethylsilane-modified silica (10.00 g)(prepared according to 3B2) was treated with an ether (100 ml) solutionof [PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ -p-OH)] (2.90 g; 4.02 mmol) at 25° C.under an argon atmosphere. The solution was agitated in a dry box for2.5 days and the resulting white solid was filtered off, washed withether (5×20 ml) and pentane (3×20 ml), and dried under reduced pressure.Yield: 12.21 g. v (N--H) 3240 cm⁻¹ (w). ²⁹ Si CPMAS: --O--SiHPh-OSilica(s, -7.7 ppm).

C3. Preparation of the silica-supported anilinium borate,w/di-ethylsilane functionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄-p-O--SiEt₂ -Osilica))⁻

An ether (100 ml) slurry of diethylsilane-modified silica (10.00 g)(prepared according to 3B3) was treated with an ether (100 ml) solutionof [PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ -p-OH)] (2.90 g; 4.02 mmol) at 25 C.under an argon atmosphere. The solution was agitated in a dry box for2.5 days and the resulting white solid was filtered off, washed withether (5×20 ml) and pentane (3×20 ml), and dried under reduced pressure.

C4. Preparation of the silica-supported anilinium borate,w/phenyl-methylsilane functionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄-p-O--SiMePh-Osilica))⁻

An ether (100 ml) slurry of phenylmethylsilane-modified silica (10.00 g)(prepared according to 3B4) was treated with an ether (100 ml) solutionof [PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ -p-OH)] (2.90 g; 4.02 mmol) at 25 C.under an argon atmosphere. The solution was agitated in dry box for 2.5days and the resulting white solid was filtered off, washed with ether(5×20 ml) and pentane (3×20 ml), and dried under reduced pressure.

C5. Preparation of the silica-supported anilinium(4-hydroxyphenyl)tris(pentafluoro-phenyl)borate, w/diphenylsilanefunctionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄ -p-O--SiPh₂ -Osilica))⁻

An ether (100 ml) slurry of diphenylsilane-modified silica (10.00 g)(prepared according to 3B5) was treated with an ether (100 ml) solutionof [PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ -p-OH)] (2.90 g; 4.02 nmmol) at 25 C.under an argon atmosphere. The solution was agitated in dry box for 2.5days and the resulting white solid was filtered off, washed with ether(5×20 ml) and pentane (3×20 ml), and dried under reduced pressure.

C6. Preparation of silica-supported anilinium(4-(4'-hydroxyphenyl)phenyl)tris(pentafluorophenyl)borate borate,w-phenylsilane functionalizer [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄-p-O--SiHPh-Osilica)]⁻

An ether (80 ml) slurry of phenylsilane-modified silica (4.00 g) wastreated with dimethylanilinium(4-(4'-hydroxyphenyl)-phenyl)tris(pentafluorophenyl)borate [PhMe₂ NH]⁺[(C₆ F₅)₃ B(C₆ H₄ -p-OH)]⁻ (prepared according to 1A2(a-d) (1.20 g; 1.49mmol) at 25 C. under an argon atmosphere. The solution was agitated indry box for 2 days and the resulting white solid was filtered off,washed with ether (5×20 ml) and pentane (3×20 ml), and dried underreduced pressure. Yield: 5.04 g. DRIFTS IR: v (Si--H) 2191 cm⁻¹ (m): v(N--H) 3244 cm³¹ 1 (w). ²⁹ Si CPMAS: --O--SiHPh-OSilica (s, -41 ppm). ¹³C CPMAS: NHMe₂ Ph (s, 47.7 ppm). ICP boron content: 0.225 percent

C7. Preparation of the dimethylsilane functionalized silica-supporteddimethylanilinium(4-(4'hydroxyphenyl)phenyl)tris(pentafluoro-phenylborate, [PhMe₂ NH]⁺[(C₆ F₅)₃ B(C₆ H₄ -p-O--SiMe₂ -OSilica)]⁻

An ether (60 ml) slurry of dimethylsilane-modified silica (1.0 g) wastreated with [PhMe₂ NH]⁺ [(C₆ F₅)₃ B(C₆ H₄ --C₆ H₄ -p-OH)]⁻ (0.39 g;0.49 mmol) at room under an argon atmosphere. The solution was agitatedin dry box for 2 days and the resulting white solid was filtered off,washed with ether (3×20 ml) and pentane (3×10 ml), and dried underreduced pressure. Yield: 1.20 g. DRIFTS IR: v (N--H) 3142 cm⁻¹ (w). ²⁹Si CPMAS: --O--SiHPh-OSilica (s, -7.6 ppm). ICP boron content: 0.232percent.

D. Slurry Batch Reactor Polymerization 1) Copolymerization

A 2 liter autoclave reactor was evacuated at 70° C. for 90 minutes priorto use. Heptane (550 ml) containing 13 μmole of triisobutylaluminum(0.013 ml; 1.0 M in toluene) was divided into two approximately equalportions and placed into two 600 ml high pressure containers. Onecontainer was treated with 35 ml of 1-hexene. The second container wastreated with 0.2 ml of a toluene solution ofbis(n-butylcyclopentadienyl)zirconium dichloride (n-BuCp)₂ ZrCl₂, (0.2mg; 0.494 μmole) and the activated support of 3C1 (12 mg; 2.4 μmolebased on boron). The hexene containing solution was transferred into thepreheated reactor followed by the catalyst mixture. Ethylene was quicklyadmitted at 125 psi (860 kPa) and the reactor was maintained at 70° C.via a recirculating water bath. Ethylene was fed on demand via a massflow controller. The reaction was continued under these reactionconditions for one hour. Polymer yield was 97 g, giving a productivity(g polymer/g Zr-hr.) of 2.15×10⁶, and a catalyst activity (g polymer/gcatalyst-hr.) of 7950.

D2-6) Additional Batch Slurry Polymerizations

The reaction conditions of Example 3D1 were substantially repeated usingdifferent quantities of bis(n-butylcyclopentadienyl)-zirconiumdichloride, triisobutyl aluminum (TIBAL) and hexene as well as differenttypes and quantities of activated supports. Results are contained inTable 1.

                  TABLE 1                                                         ______________________________________                                             Complex  Activated                                                                              TIBAL hexene                                                                              Yield                                                                              Prod..sup.1                           Run  mg (μmol)                                                                           Support  μmol                                                                             ml    g    (×10.sup.6)                                                                   Act..sup.2                      ______________________________________                                        3D2  0.2 (0.5)                                                                              3C2      12    35    41   0.9   3360                            3D3  0.2 (0.5)                                                                              3C2      13    35    40   0.9   3570                            3D4  0.4 (1.0)                                                                              3C6      20    40    137  1.5   6720                            3D5  1.0 (2.5)                                                                              3C7      30    20    87   0.4   2810                            3D6  0.2 (0.5)                                                                              3C6      13    70    73   1.6   5530                            ______________________________________                                         .sup.1 Productivity g polymer/g Zrhr                                          .sup.2 Activity g polymer/g catalysthr.                                  

D7) Ethylene Homopolymerization

a) A 2 liter autoclave reactor was evacuated at 70° C. for 90 minutesprior to use. Heptane (350 ml) containing 25 μmole oftriisobutylaluminum (0.025 ml; 1.0 M in toluene) and 1.0 ml of a toluenesolution of bis(cyclopentadienyl)zirconium dimethyl Cp₂ ZrMe₂, (0.9 mg;3.7 μmole) and the activated support of 3C6 (30 mg; 5.0 μmole based onboron was transferred into the preheated reactor. Ethylene was quicklyadmitted at 180 psi (1200 kPa) and the reactor was maintained at 80° C.via a recirculating water bath. Ethylene was fed on demand via a massflow controller. The reaction was continued under these reactionconditions for one hour. Polymer yield was 160 g. Mw=155,000,Mw/Mn=2.05, Tm (DSC) was 138° C.

b) The reaction conditions of 3D3a) were substantially repeatedexcepting that the quantity of triisobutyl aluminum was 50 μmol, thetransition metal compound was biscyclopentadienylzirconium dichloride,(2 mg, 6.8 μmol), the activated support was 3C6 (60 mg, 12 μmol based onboron), and the temperature was maintained at 75° C. Polymer yield was139 g. Mw=144,000, Mw/Mn=2.41, Tm (DSC) was 135° C.

c) The reaction conditions of 3D23) were substantially repeatedexcepting that the quantity of triisobutyl aluminum was 100 μmol, thetransition metal compound was (t-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitanium dichloride, (10 mg, 27.2 μmol), theactivated support was 3C1 (200 mg, 40 μmol based on boron), and theethylene pressure was 200 psi (1400 kPa). Polymer yield was 94.2 g.Mw=961,000, Mw/Mn=2.00, Tm (DSC) was 135° C.

d) The reaction conditions of 3D3a) were substantially repeatedexcepting that the quantity of triisobutyl aluminum was 50 μmol, thetransition metal compound was bisindenylzirconium dichloride, (2 mg, 4.8μmol), and the activated support was 3C1 (80 mg, 13 μmol based on boron.Polymer yield was 140 g.

Example 4 C. Preparation of phenylsilane functionalized silica supportedanilinium (6-hydroxy-2-naphthyl)tris(pentafluorophenyl)borate, [PhMe₂NH]⁺ [silica-OSiPhH--O-6-C₁₀ H₆ -2-B(C₆ F₅)₃ ]⁻

A mixture of 1.67 g [PhMe₂ NH]⁺ [6-HOC₁₀ H₆ -2-B(C₆ F₅)₃ ] (preparedaccording to Example 1A3) and 5.0 g phenylsilane-modified silica(prepared according to Example 1B) were heated at gentle reflux withmechanical stirring for 24 hours. The solids were collected byfiltration, washed with Et₂ O and pentane, and dried under reducedpressure. CP-MAS ²⁹ Si NMR: -43 ppm. Solids were determined to be 0.154weight percent boron.

D. Slurry Batch Reactor Polymerizations

D1. A 2-L autoclave was evacuated at 80° C. overnight prior to use. Aheptane (300 mL) slurry of phenylsilane modified-silica supporteddimethylanilinium (6-hydroxy-2-naphthyl)tris(pentafluoro-phenyl)borate[PhMe₂ NH]⁺ [silica-OSiPhH--OC₁₀ H₆ -2-B(C₆ F₅)₃ ]⁻ (0.100 g),(t-butylamido)dimethyl(tetramethyl-η⁵ -cyclopentadienyl)silanetitaniumdimethyl (5 mg), and 0.1 mL of a 25 percent Et₃ Al solution in heptanewere transferred into the preheated reactor. Ethylene was quicklyinjected to 180 psi (1200 kPa) and the reactor was maintained at 80° C.via a recirculating water bath. Ethylene was fed on demand via a massflow controller. Polyethylene yield after 60 minutes was 50 g.

D2. The procedure of example 4D1) was repeated with the followingchanges: 0.05 g [PhMe₂ NH]⁺ [silica-OSiPhH--OC₁₀ H₆ -2-B(C₆ F₅)₃ ]⁻,0.05 mL Et₃ Al solution, 1.5 mg Cp₂ ZrMe₂, and 3 psi (20 kPa) H₂.Polyethylene yield alter 60 minutes was 144 g.

D3-22. The previous reaction conditions were substantially repeatedusing transition metal complexes, activated supports, and other reactionconditions indicated in Table 2. Results are contained in Table 2.Molecular weights were determined by gel permeation chromatography(GPC).

                                      TABLE 2                                     __________________________________________________________________________                          C.sub.8 H.sub.16.sup.1                                                            H.sub.2                                                                          time                                                                             Yield                                                                            Mw Mw/                                     Run                                                                              Support                                                                           complex (μmol)                                                                     Scav. (mmol)                                                                         ml  kPa                                                                              min.                                                                             (g)                                                                              ×10.sup.-6                                                                 Mn                                      __________________________________________________________________________    4D3                                                                              4C  TM.sup.2 (30)                                                                         TEA.sup.3 (1.5)                                                                       0  14 60 48 -- --                                      4D4                                                                              "   TP.sup.4 (30)                                                                         TEA (1.5)                                                                            "   "  "  74 1.13                                                                             6.1                                     4D5                                                                              "   "       TEA (.75)                                                                            "   "  "  62 1.08                                                                             4.9                                     4D6                                                                              "   "       TEA (.38)                                                                            "   "  "  46 1.03                                                                             4.9                                     4D7                                                                              "   "       TEA (.05)                                                                            "   "  "  9  -- --                                      4D8                                                                              "   "       TEA (1.5)                                                                            "   "  "  61 -- --                                      4D9                                                                              "   "       MAO.sup.5 (.05)                                                                      "   "  "  4  -- --                                      4D10                                                                             "   "       TEA (1.5)                                                                            "   35 "  52 0.73                                                                             5.8                                     4D11                                                                             "   "       TEA (1.5)                                                                            "   60 "  52 0.79                                                                             4.9                                     4D12                                                                             1C  "       TEA (1.5)                                                                            "   280                                                                              "  39 0.40                                                                             13.5                                    4D13                                                                             "   "       TEA (1.5)                                                                            "   "  "  26 --                                         4D14                                                                             "   TP (54) TEA (1.5)                                                                            "   14 42 214                                                                              --                                         4D15                                                                             "   TP (45) TEA (1.5)                                                                            50  28 60 98 0.60                                                                             7.3                                     4D16                                                                             "   TP (45) TEA (1.5)                                                                            25  34 "  125                                                                              0.80                                                                             6.2                                     4D17                                                                             "   TP (90) TEA (1.5)                                                                            50  70 "  62 0.40                                                                             14.2                                    4D18                                                                             "   TP (90) TEA (1.5)                                                                            35  "  "  240                                                                              0.75                                                                             8.6                                     4d19                                                                             "   ZC.sup.6 (68)                                                                         TBAL.sup.7 (.7)                                                                          140                                                                              "  106                                                                              0.04                                                                             2.0                                     4d20                                                                             "   RI.sup.8 (5)                                                                          TBAL (.2)  "  30 169                                                                              -- --                                      4D21                                                                             3C6 ZB.sup.9 (10)                                                                         TBAL (.2)                                                                             0  "  "  4  -- --                                      4D22                                                                             4C  "       TBAL (.2)                                                                            30  "  "  142                                                                              -- --                                      __________________________________________________________________________     .sup.1 1octene                                                                .sup.2                                                                        (tbutylamido)dimethyl(tetramethyl-η.sup.5cyclopentadienyl)silanetitan    um dimethyl                                                                    .sup.3 triethylaluminum                                                       .sup.4                                                                        (tbutylamido)dimethyl(tetramethyl-η.sup.5cyclopentadienyl)silanetitan    um (II) 1,3pentadiene                                                          .sup.5 triisobutylaluminum modified methylalumoxane                           .sup.6 biscyclopentadienylzirconium dichloride                                .sup.7 triisobutylaluminum                                                    .sup.8 racbis(indenyl)zirconium (II) 1,4diphenylbutadiene (prepared by        reduction of the corresponding dichloride in the presence of                  1,4diphenyl-1,3-butadiene).                                                   .sup.9 bis(nbutylcyclopentadienyl)zirconium dichloride                   

Example 5 Preparation of dimethylsilane-modified alumina

5.0 g of Pural™ 200 alumina (available from Condea Chemie AG (calcinedat 600° C. under vacuum) was slurried in 25 mL of pentane, and 4.5 mL (5mmol/g) HMe₂ SiNHSiMe₂ H was added. The mixture was shaken for 15 hours.The solids were collected on a fritted funnel, washed with pentane, anddried under reduced pressure. DRIFTS IR: 2958, 2904 (C--H), 2102 (br,Si--H) cm⁻¹.

Preparation of the activated support by reaction of dimethylsilanefunctionalized alumina with dimethylanilinium4-(hydroxyphenyl)-tris(pentafluorophenyl)borate, [PhMe₂ NH]⁺ [(C₆ F₅)₃B(C₆ H₄ -p-OSiMe₂ O-alumina)].sup.-

1.0 g dimethylsilane-modified alumina was slurried with 0.35 g [PhMe₂NH]⁺ [(C₆ F₅)₃ B(C₆ H₄ -p-OH)] in 10 mL Et₂ O for 12 hours. At this timethe solids were collected by filtration, washed with Et₂ O and pentane,and dried under reduced pressure. DRIFTS IR: 2960, 2908 (C--H) 2131(Si--H), 1641, 1623, 1591, 1514, 1461, 1261 (aromatic ring breathing)cm⁻¹.

Slurry Batch Reactor Polymerization

A 2-L autoclave was evacuated at 80° C. overnight prior to use. Aheptane (300 mL) slurry of PhMe₂ NH[(C₆ F₅)₃ B(C₆ H₄ -p-OSiMe₂O-alumina)] (0.200 g), Cp₂ ZrMe₂ (10), and 0.2 mL of a 25 percent Et₃ Alsolution in heptane were transferred into the preheated reactor.Ethylene was quickly injected to 180 psi (1200 kPa) and the reactor wasmaintained at 80° C. via a recirculating water bath. Ethylene was fed ondemand via a mass flow controller. Polyethylene yield after 60 minuteswas 2.16 g.

Example 6 D1-5 Continuous Slurry Polymerization

A continuous slurry polymerization was carried out using a computercontrolled 10 L slurry reactor equipped with an external water jacket, astirrer, a thermocouple, a catalyst addition dip-tube, diluent additiondip-tube, and a continuous capacitance, level detector probe. Purifiedisopentane diluent was set to a constant flow of 4000 g/hr whichresulted in maintaining a solids content in the reactor of approximately60 weight percent. The reactor level was maintained at approximately 60percent of the reactor volume by periodic removal of the reactorcontents. The reactor was heated to a temperature of 55° C. A hydrogenflow of 0.15 L/hr, an ethylene flow of 650 g/hr and a 1-butene flow of75 g/hr were initiated and the reactor pressure set to 220 psi (1.5Mpa). The catalyst mixture was prepared by combining 81 mg (200 μmol) of(n-BuCp)₂ ZrCl₂, 4.90 g of phenylsilane modified silica supporteddimethylanilinium4-(4'-hydroxyphenyl)phenyl)tris(pentafluorophenyl)borate preparedaccording to preparation 3C6, and 2 mmol triisobutylaluminum (TIBA) in800 mL of hexane in the dry box and placing the mixture in a 1 L bomb.The contents were then transferred under nitrogen to the stirredcatalyst vessel and diluted to 8 L with isopentane. The catalyst mixturewas slowly added to the reactor from the continuously stirred catalysttank. The ethylene and 1-butene flows were then incrementally increased.A portion of the reactor contents was periodically passed by means ofexit valves to a heated flash vessel wherein diluent was removed. Thedevolatilized polymer's properties were measured and recorded. Thereactor was operated continuously over an 8 hour period. The datareported in Table 3 were measured on samples obtained after the reactorreattained equilibrium following a change in process conditions.

                                      TABLE 3                                     __________________________________________________________________________       C.sub.2 H.sub.4                                                                  C.sub.4 H.sub.8                                                                  Kg PE                                                                             yield                                                                            I2  Mw     Density                                                                           C.sub.4 H.sub.8                                                                   Bulk δ                               Run                                                                              g/hr                                                                             g/hr                                                                             g Ti                                                                              (g)                                                                              dg/min                                                                            ×10.sup.-6                                                                 Mw/Mn                                                                             (δ) g/cc                                                                    mol %                                                                             g/cc                                       __________________________________________________________________________    6D1                                                                              650                                                                              75 0.36                                                                              206                                                                              0.06       0.9471                                                                            <0.2                                           6D2                                                                              850                                                                              100                                                                              0.51                                                                              339                                                                              0.6        0.9354                                                                            0.57                                           6D3                                                                              850                                                                              100                                                                              0.51                                                                              320                                                                              2.22                                                                              0.101                                                                            2.21                                                                              0.9321                                                                            1.16                                                                              0.35                                       6D4                                                                              1000                                                                             138                                                                              0.64                                                                              414                                                                              2.71       0.9310                                                                            1.52                                           6D5                                                                              1000                                                                             138                                                                              0.64   1.46                                                                              0.125                                                                            2.93                                                                              0.9316  0.32                                       __________________________________________________________________________

D6-14 Continuous Slurry Polymerizations Preparation ofbis(n-butylcyclopentadienyl)zirconium (1,4-diphenylbutadiene)

Under nitrogen, recrystallized bis(n-butylcyclopentadienyl)zirconiumdichloride (2.02 g, 4.99 mmol) was slurried in hexane with 1,4-diphenylbutadiene. A solution of n-BuLi in hexanes (2.5 M, 2.05 mL, 5.13 mmol)was added and a deep red color formed immediately. After stirring for 30minutes at room temperature, the mixture was refluxed for 2 h. Thesolvent was removed in vacuo and the solid redissolved in about 20 mL ofhot hexane. Red crystals formed. A small amount of hexane was added andthe reaction flask was cooled in a freezer and then filtered through amedium frit. The red crystals were isolated via filtration through amedium frit funnel, washed once with cold hexane, and dried in vacuo(2.04 g, 76.5 percent yield).

Polymerizations

The reaction conditions of Examples 6D1-5 were substantially repeatedexcepting that the purified isopentane was set to a constant flow of2500 g/hr, the reactor temperature was 65° C., and the initial ethyleneand 1-butene flows were 1000 g/hr and 50 g/hr respectively. The initialcatalyst mixture was prepared by combining 40.5 mg (100 μmol) of(n-BuCp)₂ ZrCl₂, 2.45 g of phenylsilane modified silica supporteddimethylanilinium4-(4'-hydroxyphenyl)phenyl)tris(pentafluorophenyl)borate preparedaccording to preparation 3C6, and 1 mmol TIBA in 400 mL of hexane in thedry box and placing the mixture in a 1 L bomb. The contents were thentransferred under nitrogen to the stirred catalyst vessel and diluted to8 L with isopentane. The catalyst mixture was slowly added to thereactor from a continuously stirred catalyst tank. The ethylene and1-butene flows were then incrementally changed. A second, stirredcatalyst vessel was prepared in the same manner as above described andthe two catalyst vessels were switched back and forth every 3-5 hrduring the 34 hour polymerization. During the polymerization themetallocene catalyst precursor was changed tobis(n-butylcyclopentadienyl)zirconium (II) (1,4-diphenylbutadiene),(n-BuCp)₂ Zr(PhCH═CHCH═CHPh). Results are shown in Table 4.

                                      TABLE 4                                     __________________________________________________________________________           H.sub.2                                                                          C.sub.2 H.sub.4                                                                  Kg PE                                                                             I2  Mw     Density                                                                           C.sub.4 H.sub.8                                                                   Bulk δ                              Run                                                                              Cat.                                                                              g/hr                                                                             g/hr                                                                             g Ti                                                                              dg/min                                                                            ×10.sup.-6                                                                 Mw/Mn                                                                             (δ) g/cc                                                                    mol %                                                                             g/cc                                      __________________________________________________________________________    6D6                                                                              Zr(IV).sup.1                                                                      0.15                                                                             100                                                                              0.61                                                                              0.306      0.9389                                            6D7                                                                              Zr(IV)                                                                            0.15                                                                             100                                                                              0.61                                                                              0.325      0.9359                                            6D8                                                                              Zr(IV)                                                                            0.15                                                                             100                                                                              0.61                                                                              1.638      0.9304                                            6D9                                                                              Zr(IV)                                                                            0.15                                                                             100                                                                              0.61                                                                              2.099      0.9285                                                                            1.54                                                                              0.37                                      6D10                                                                             Zr(IV)                                                                            0.15                                                                             100                                                                              0.61                                                                              2.408                                                                             0.092                                                                            2.098                                                                             0.9305                                                                            1.70                                                                              0.37                                      6D11                                                                             Zr(IV)                                                                            0.075                                                                            172                                                                              1.00                                                                              5.24                                                                              0.075                                                                            2.1 0.9242                                                                            2.79                                                                              0.36                                      6D12                                                                             Zr(II).sup.2                                                                      0.075                                                                            172                                                                              0.80                                                                              4.57                                                                              0.076                                                                            2.073                                                                             0.9230                                                                            2.86                                                                              0.35                                      6D13                                                                             Zr(II)                                                                            0.075                                                                            172                                                                              0.80                                                                              3.085                                                                             0.083                                                                            2.181                                                                             0.9141                                                                            4.76                                                                              0.35                                      6D14                                                                             Zr(II)                                                                            0.075                                                                            250                                                                              0.81                                                                              2.058                                                                             0.092                                                                            2.197                                                                             0.9126                                                                            4.82                                                                              0.34                                      __________________________________________________________________________     .sup.1 bis(nbutylcyclopentadienyl)zirconium dichloride                        .sup.2 bis(nbutylcyclopentadienyl)zirconium (1,4diphenylbutadiene)       

Example 7 B Preparation of triisobutylaluminum treated phenylsilanemodified silica

B1. Phenylsilane modified silica was prepared substantially according tothe procedure of Example 1B excepting the silica was Sylopol™ 2212silica and the calcining temperature was 400° C. A heptane (200 ml)slurry of this phenylsilane modified silica (10 g), was treated withTIBA (20 ml, 1M in toluene) at room temperature. The resulting mixturewas agitated in a shaker for 12 h and was then filtered, washed withpentane (3×50 ml), and dried in vacuo. Yield: 11.3 g. DRIFTS IR: v(Si--H) 2170 cm⁻¹ (m). ²⁹ Si CPMAS: d -24 ppm.

B2. The above reaction conditions were substantially repeated exceptingthat the silica (Sylopol™ 2212) was calcined at 800° C.

B3. The above reaction conditions were substantially repeated exceptingthat the silica (Sylopol™ 2212) was calcined at 500° C.

B4. The above reaction conditions were substantially repeated exceptingthat the silica (Sylopol™ 2212) was calcined at 300° C.

C. Preparation of triisobutylaluminum treated, phenylsilane modifiedsilica-supported N,N-dimethyl anilinium(4-(4'-hydroxyphenyl)phenyl)trispentafluorophenyl-borate-[PhMe₂ NH]⁺[(C₆ F₅)₃ B(C₆ H₄ --C₆ H₄ -p-O--SiPhH--OSi)]⁻

C1. A diethylether (200 mnl) slurry of the TIBA modified phenylsilanesilica (7B1) was treated with [PhMe₂ NH][(C₆ F₅)₃ B(C₆ H₄ --C₆ H₄-p-OH)] (3.01 g; 3.75 mmol) at room temperature under argon atmosphere.The solution was agitated in dry box for 2 days and the resulting whitesolid was filtered off, washed with ether (3×50 ml) and pentane (3×10ml), and dried in vacuo. Yield: 11.25 g. ICP boron content: 0.244 wtpercent.

C2. The preparation of C1 was substantially shortened (2-3 hoursreaction time) using hot toluene in place of diethyl ether.

C3. The preparation of C1 was substantially repeated using thetriisobutylaluminum treated phenylsilane modified silica of 7B4.

D. Ethylene Homopolymerizations

D1. A 2 liter autoclave reactor was evacuated at 75° C. for 90 min priorto use. A supported tethered catalyst was prepared by combining TIBA(100 mmole; 0.1 ml; 1.0 M in toluene), heptane (˜500 ml) andbis(n-butylcyclopentadienyl)zirconium dichloride (^(n) BuCp)₂ ZrCl₂ (0.1mg, 0.247 mmol), followed by the addition of the TIBA treated,phenylsilane modified silica supported anilinium(4-(4'-hydroxyphenyl)phenyl)-tris(pentafluorophenyl)borate of 7C1 (7 mg;1.58 mmol). The catalyst mixture was transferred into the preheatedreactor via vacuum line. Ethylene was quickly admitted to 180 psi (1.2Mpa), and the reactor was maintained at 75° C. via a recirculating waterbath. Ethylene was fed on demand via a mass flow controller. Polymeryield: 180 g (1 hr). M_(w) =169,000, M_(w) /M_(n) =2.11. Productivity:8.0×10⁶ g.PE/g.Zr.h.

D2. The reaction conditions of 7D1 were substantially repeated exceptingthat the tethered borate support was phenylsilane modified silicasupported anilinium(4-(4'-hydroxyphenyl)phenyl)tris(pentafluoro-phenyl)borate (Sylopol™2212 silica, 500° C. calcining temperature (7B3)). The quantities ofreagents used were: (^(n) BuCp)₂ ZrCl₂ (0.2 mg, 0.494 mmol), TIBA (100mmole; 0.1 ml; 1.0 M in toluene), and tethered borate (12 mg; 1.97mmol). Polymer yield: 204 g (1 hr). M_(w) =184,000, M_(w) /M_(n) =2.38.Productivity: 4.5×10⁶ g.PE/g.Zr.h.

D3. The reaction conditions of 7D1 were substantially repeated exceptingthat the tethered borate support was phenylsilane modified silicasupported anilinium (4-hydroxyphenyl)tris(pentafluoro-phenyl)borate(Sylopol™ 2212 silica, 800° C. calcining temperature (7B2)). Thequantities of reagents used were: (^(n) BuCp)₂ ZrCl₂ (0.2 mg, 0.494mmol), TIBA (100 mmole; 0.1 ml; 1.0 M in toluene), and tethered borate(13.5 mg; 2.16 mmol). Polymer yield: 208 g (1 hr). M_(w) =156,000, M_(w)/M_(n) =2.09. Productivity: 4.6×106 g.PE/g.Zr.h.

D4. A 2 liter autoclave reactor was evacuated at 80° C. for 90 min priorto use. TIBA (350 mmole; 0.35 ml; 1.0 M in toluene) was added to heptane(˜500 ml) and the solution treated with(t-butylamido)dimethyl-(tetramethyl-η⁵ -cyclopentadienyl)silane-titaniumdichloride (0.5 mg, 1.36 mmol) followed by the addition of the tetheredborate of 7C1 (40 mg; 8.5 mmol). The catalyst mixture was transferredinto the preheated reactor via vacuum lines. Ethylene was quicklyadmitted to 200 psi (1.4 Mpa) and the reactor was maintained at 80° C.via a recirculating water bath. Ethylene was fed on demand via a massflow controller. Polymer yield: 67.7 g (1 hr). Mw=3.22×10⁶, Mw/Mn=2.96.Productivity: 1.0×10⁶ g.PE/g Ti.h

D5. The reaction conditions of 7D4) were substantially repeated usingthe metallocene ethylenebis(indenyl)zirconium dichloride and thetriisobutylaluminum treated, phenylsilane modified silica supportedborate of 7C3. The reagents were: (EBI)ZrCl₂ (0.13 mg, 0.319 mmol), TIBA(100 mmole; 0.1 ml; 1.0 M in toluene), and TIBA treated, phenylsilanemodified, silica supported tethered borate (9.8 mg; 1.54 mmol).Polymer.sup.∘ yield: 170 g (1 hr). M_(w) =130,000 M_(w) /M_(n) =2.63.Productivity: 5.9×10⁶ g.PE/g.Zr.h.

What is claimed is:
 1. A support for use in preparing supportedcatalysts for addition polymerizations comprising the reaction productof:(A) an inorganic oxide material comprising a solid matrix selectedfrom the group consisting of porous silicas, aluminas, aluminosilicates,aluminophosphates, clays, titanias, and mixtures thereof, and reactivesilane functionalized derivatives of hydroxyl groups on the surfacethereof, said reactive silane functionalized derivatives of hydroxylgroups corresponding to the formula:

    --OSiR.sub.2 H,

wherein R, independently each occurrence, is hydrogen, or C₁₋₂₀hydrocarbyl, said inorganic oxide material comprising less than 1.0 mmolof hydroxyl groups per gram, and (B) an activator compoundcomprising:b₁) a cation which is capable of reacting with a transitionmetal compound to form a catalytically active transition metal complex,and b₂) a compatible anion containing at least one substituent able toreact with the silane functionalized derivatives of hydroxyl groups onthe surface of the inorganic oxide material, thereby covalently bondingthe compatible anion to the support.
 2. A support according to claim 1wherein the inorganic oxide is silica.
 3. A support according to claim 1wherein the activator compound is a salt of the formula:

    (G.sup.+e)(DM'Q.sub.3).sup.-.sub.e,

wherein G^(+e) is the cationic remnant of a Bronsted acid salt, anoxidizing cation, a carbonium ion or a silylium ion; [DM'Q₃ ]⁻ is anoncoordinating, compatible anion, D is a linking group comprising afunctional group capable of reaction with the inorganic oxide material,with residual hydroxyl functional group, thereof, or with said reactivesilane functionalized derivatives of hydroxyl groups thereof, M' isboron or aluminum in an oxidation state of 3; Q is a hydrocarbyl-,hydrocarbyloxy-, fluorinated hydrocarbyl-, fluorinated hydrocarbyloxy-,or fluorinated silylhydrocarbyl group of up to 20 nonhydrogen atoms, ande is an integer from 1 to
 3. 4. A support according to claim 3 wherein eis
 1. 5. A support according to claim 3 where:M' is boron; and Q ispentafluorophenyl.
 6. A support according to claim 1 wherein the anionof the activator is selected from the group consisting oftris(pentafluorophenyl)(4-hydroxyphenyl)borate,tris-(2,4-difluorophenyl)(4-hydroxyphenyl)borate,tris-(3,5-difluorophenyl)(4-hydroxyphenyl)borate,tris-(3,5-di-trifluoromethylphenyl)(4-hydroxyphenyl)borate,tris(pentafluorophenyl(2-hydroxyethyl)borate,tris(pentafluorophenyl))(4-hydroxybutyl)borate,tris(pentafluoro-phenyl)(4-hydroxycyclohexyl)borate,tris(pentafluorophenyl)(4-hydroxy-2,6-dimethylphenyl)borate,tris(pentafluorophenyl)4-(4'-hydroxyphenyl)phenylborate,tris(pentafluorophenyl)4-(4'-hydroxy-2',6'-dimethylphenyl)phenylborate,and tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate.
 7. A supportedcatalyst comprising the support of claim 1 and (C) a transition metalcompound containing at least one π-bonded anionic ligand group and asubstituent capable of reacting with the activator compound to therebyform a catalytically active transition metal complex.
 8. A supportedcatalyst according to claim 7 wherein the π-bonded anionic ligand groupof the transition metal compound (C) is a conjugated or nonconjugated,cyclic or non-cyclic dienyl group, an allyl group, aryl group, or asubstituted derivative thereof.
 9. A supported catalyst according toclaim 8 wherein the π-bonded anionic ligand group is a cyclopentadienylgroup or a substituted derivative thereof.
 10. A supported catalystaccording to claim 7 wherein the transition metal is titanium, zirconiumor hafnium.
 11. A supported catalyst according to claim 7 additionallycomprising an alumoxane, or a hydrocarbylaluminum compound according tothe formula AlR₃ wherein R is C₁₋₂₀ hydrocarbyl or hydrocarbyloxy. 12.An addition polymerization process wherein one or more additionpolymerizable monomers are contacted with a supported catalyst accordingto claim 7 under addition polymerization conditions.
 13. The additionpolymerization process according to claim 12 carried out under slurry orgas phase polymerization conditions.
 14. A gas phase additionpolymerization process according to claim 13 wherein condensed monomeror inert diluent is present.